CN110183576A - A kind of emulsifier, preparation method and the application of the production polybutadiene latex can be used for agglomeration - Google Patents
A kind of emulsifier, preparation method and the application of the production polybutadiene latex can be used for agglomeration Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/14—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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Abstract
The present invention relates to the preparation method and applications of a kind of emulsifier of production polybutadiene latex that can be used for agglomeration, emulsifier.The emulsifier includes hydrophilic sorb alcoholic extract hydroxyl group, amide groups and hydrophobic alkyl carbon chain, isopropyl.Reach good stable reaction effect using the amphipathic good performance of the emulsifier low temperature as the emulsifier that polybutadiene latex produces, meanwhile, achieve the effect that control polybutadiene latex agglomeration using the characteristic of the amphipathic difference of its high temperature；Particle after agglomeration may make to achieve the purpose that particle diameter distribution is narrow by precise control of temperature.
Description
Technical field
The invention belongs to engineering plastics ABS production technical field, in particular to a kind of production polybutadiene that can be used for agglomeration
Emulsifier, preparation method and the application of alkene latex.
Background technique
ABS resin is a kind of important engineering plastics, using and its extensively.It is by butadiene, styrene and acrylonitrile three
Member copolymerization obtains.
Two methods of continuous bulk and emulsion graft polymerization-ontology SAN blending method is widely used in the method for preparing ABS at present.
Emulsion graft polymerization-ontology SAN blending method has the advantage that technologically advanced, product scope is wide, performance is good, pollution is small at this stage, becomes
The main stream approach of ABS production.
Emulsion graft polymerization-ontology SAN blending method, production stage is: polymerizing butadiene being produced polybutadiene glue first
Polybutadiene latex, then polymerize by newborn (PBL) with styrene and acrylonitrile grafting, and ABS grafting powder is obtained after cohesion is dry
Material, ABS grafting powder are granulated with the SAN resin blending of substance law production obtain ABS resin again.
In order to obtain high impact resistance, the partial size of polybutadiene latex needs to reach 300-400nm, wherein one-step method system
Standby 300-400nm butadiene latex, polymerization time generally will be at 40-60 hours.Therefore, it is agglomerated by small particle butadiene
The method of big partial size butadiene (that is: first synthesizes small particle base latex, then loses its part by method physically or chemically
Stability is gone, to make latex particle that controllable aggregation occur, reaches and increases particle size effect) become production polybutadiene latex
Main stream approach.
Common agglomeration method has physics agglomeration technique (such as: freezing agglomeration, Pressure agglomeration) and chemical agglomeration, and (such as: soda acid is attached
Poly-, salt agglomeration, macromolecule agglomeration).Such as in patent CN1840556, the poly- fourth of big partial size is prepared as agglomerant using acetic acid
Diene rubber latex in patent US4804694, prepares large-particle-size styrene-butadiene latex, patent using the inorganic salts agglomeration such as potassium chloride
By the way that the water-soluble amphipathic copolymeric being made of at least one hydrophilic segment and at least one hydrophobic part is added in CN1217958C
The aqueous solution of object makes the latex agglomeration of dispersion, and patent US2002198309 is disclosed with butadiene-propylene acetoacetic ester-metering system
Acid copolymer latex is that macromolecule agglomerant increases large-sized method.Physics agglomeration technique (such as: freezing, high pressure) is to equipment requirement
It is higher；Chemical agglomeration method, particle size are restricted, and temperature, time effects are big, it is more difficult to control.Macromolecule agglomeration technique is by added
If polymer substance type limits, broad particle distribution after agglomeration, and emulsifier is added after needing.
Due to that will introduce agglomerant in traditional agglomeration process, and the lotion of agglomeration process is metastable state, emulsion particle
Original stability is broken, and microcosmic phase emulsion particle particle buildup merges so that polybutadiene latex partial size was grown up rapidly
Process, emulsion particle partial size when assembling fusion is difficult to control accurately, therefore causes particle diameter distribution wide, influences final ABS product
Toughening effect.
Summary of the invention
The purpose of the present invention is for introducing agglomerant and poly- fourth obtained in agglomeration process existing in the prior art
Diene latex particle size is distributed wide problem, provides a kind of new emulsifier, can be used in butadiene latex production process
Emulsification polybutadiene latex grain makes emulsion-stabilizing, and agglomerant can be served as in agglomeration process；Using it to polybutadiene latex
Carry out emulsification and agglomeration, the polybutadiene latex of available narrow ditribution partial size, the increasing so as to improve polybutadiene latex to ABS
Tough effect.
In order to achieve the goal above, the invention adopts the following technical scheme:
The present invention provides a kind of emulsifiers of production polybutadiene latex that can be used for agglomeration, which is characterized in that described
Emulsifier includes hydrophilic sorb alcoholic extract hydroxyl group, amide groups and hydrophobic alkyl carbon chain, isopropyl.
Emulsifier of the present invention is to carry out esterification by sorbierite single-hard ester acid ester (Span 60) and acid anhydrides, then
The amidated products generated are reacted with isopropylamine again.
Acid anhydrides of the present invention be phthalic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, diglycolic anhydride, 2,
3- pyrazine diacid acid anhydride, 1,2- cyclohexyl dicarboxylic acid acid anhydride, 4- methyl hexahydrophthalic anhydride, 1,2- cyclohexyl dicarboxylic acid acid anhydride, 1,2- ring, penta dioctyl phthalate
One of acid anhydride, 1,1- cyclohexanediacetic acid acid anhydride are a variety of, preferably phthalic anhydride and/or succinic anhydride.
The molar ratio of acid anhydrides and Span60 of the present invention is (0.9-1): 1, preferably (0.93-0.97): 1.
The molar ratio of isopropylamine of the present invention and acid anhydrides is (0.5-1): 1, preferably: (0.7-0.9): 1.
The present invention provides a kind of methods for preparing emulsifier, comprising the following steps:
(1) it is proportionally added into Span60 and organic solvent in the reactor, is heated to 70 DEG C -80 DEG C, preferably 73 DEG C -77
DEG C, acid anhydrides is added in reactor carries out esterification in proportion；
(2) isopropylamine is added simultaneously when residual carboxylic's radical content reaches consistent with acid anhydrides molal quantity is added in step (1)
It is uniformly mixed, reaction generates carboxylic acid amine salt, then removes organic solvent；
(3) 200 DEG C -260 DEG C, preferably 220 DEG C of -240 DEG C of progress acylation reactions are warming up to, to isopropylamine conversion ratio >=
It is 3Kpa-10Kpa that absolute pressure is constant when 90%, in maintenance reactor, and preferably 5Kpa-8Kpa, the reaction was continued, to product acid value
When remaining unchanged, emulsifier amidated products are obtained.
The reaction of step (1)-(3) schematically as follows, is not limited thereto:
Organic solvent of the present invention is acetonitrile, ethyl acetate, tetrahydrofuran, ethyl propionate, one in propyl acetate
Kind or a variety of, ethyl acetate.
The additional amount of organic solvent of the present invention and the mass ratio of Span 60, acid anhydrides, isopropylamine total amount are (5-
9): 1, preferably: (6-8): 1.
The present invention provides a kind of preparation methods of polybutadiene latex comprising the steps of:
(1) made from any one of emulsifier of any of claims 1-5 or claim 6-8 the method
Emulsifier, disproportionated rosin acid potassium, potassium oleate, butadiene, optional second comonomer, potassium carbonate and tert-dodecylmercaotan (TDM),
Deionized water, potassium peroxydisulfate are added in reaction kettle, are warming up to 60 DEG C -75 DEG C, preferably 65 DEG C of -70 DEG C of progress polymerization reactions；
(2) when butadiene is reacted to conversion ratio >=95%, with 0.1 DEG C/min-, 0.5 DEG C/min, preferably 0.2 DEG C/
0.4 DEG C of min-heats up, and stops reaction when partial size agglomeration to 300nm or so to get big partial size polybutadiene latex is arrived.
In step (2) of the present invention, when butadiene is reacted to conversion ratio >=95%, polybutadiene latex is obtained
Partial size is 92nm-106nm, preferably 97nm-104nm.
In step (2) of the present invention, big partial size polybutadiene latex, partial size 280nm-320nm, preferably
290nm-310nm。
The present invention is prepared in the method for polybutadiene latex, and raw materials used quality dosage is as follows:
Second comonomer of the present invention is the one or more of styrene, acrylonitrile and methyl methacrylate, preferably
Styrene and/or methyl methacrylate.
Emulsifier amidated products of the present invention, have on strand hydrophilic sorb alcoholic extract hydroxyl group, amide groups and
Hydrophobic alkyl carbon chain, isopropyl make product have temperature sensitive properties.In low temperature polymerization, emulsifier is in unfold shape,
Octadecyl carbochain rivet is stretched over water phase in polybutadiene latex grain surface, Sorbitan alcohol groups and amide group, cream
Agent is evenly distributed on polybutadiene latex grain surface and forms absorption parsing balance, maintains emulsion particle raw during polymerizing butadiene
Long stability.When the temperature increases, since hydrone warm-up movement aggravates, the isopropyl repellency for being stretched over water phase is enhanced,
Due to the effect of similar compatibility, isopropyl basal orientation octadecyl carbochain is drawn close, and in curly, emulsifier molecules incline emulsifier molecules
To being precipitated from water phase in being brought together, surface-active is lost, the unstable of emulsion particle is caused, assembles emulsion particle, thus
The agglomeration process for completing polybutadiene latex obtains big partial size polybutadiene latex.The present invention may make by precise control of temperature
Particle achievees the purpose that particle diameter distribution is narrow after agglomeration.
The beneficial effects of the present invention are: a kind of Thermo-sensitive emulsifier is provided, can either be used to produce polybutadiene glue
Cream, while having again makes latex agglomeration increase large-sized effect.Polybutadiene latex agglomeration is carried out using its Thermo-sensitive, is passed through
Precise control of temperature, the polybutadiene latex of available narrow ditribution partial size, particle diameter distribution index is less than 0.2, with its preparation
ABS product compared with agglomeration technique ABS, bending strength and bending modulus all make moderate progress, and impact strength is more than 170J/m, are protecting
Tensile strength is held not less than in the case where agglomeration technique ABS, elongation at break is more than 60%.
Specific embodiment:
Analysis instrument:
Partial size and particle size distribution index: Malvern Nano-ZS90 type particle size analyzer
Izod impact strength: 9050 type pendulum percussion instrument of CEAST
Bending strength, bending modulus, tensile strength, elongation at break: 5966 type universal testing machine of Instron
Test method:
Izod impact strength: standard ASTM D256
Bending strength, bending modulus: standard GB T9341
Tensile strength, elongation at break: standard GB T1040
The following examples will be further described method provided by the present invention, but the present invention is not limited to cited
Embodiment, should also include the present invention claims interest field in other any well known change.
Embodiment 1
(1) 473.7 parts and 2996.8 parts of acetonitrile of Span60 are added in the reactor, 80 DEG C are heated to, then to reaction kettle
99.1 parts of progress esterifications of middle addition succinic anhydride；
(2) 26.6 parts of isopropyls are added when residual carboxylic's radical content reaches consistent with acid anhydrides molal quantity is added in step (1)
Base amine is simultaneously uniformly mixed, and removes acetonitrile；
(3) 220 DEG C are warming up to, when the conversion ratio of isopropylamine >=90%, maintains in reactor that absolute pressure is constant to be
3Kpa, the reaction was continued, when product acid value remains unchanged, obtains emulsifier amidated products.
Embodiment 2-5
It is formulated according to table 1, prepares embodiment 2-5 amidated products emulsifier, remaining reaction condition and product parameters respectively
It is same as Example 1, it is mass fraction in table.
1 embodiment 1-5 raw material of table and parameter
Embodiment 6
(1) 0.8 part of emulsifier obtained, 1.2 parts of disproportionated rosin acid potassium, 0.8 part of potassium oleate, butadiene in Example 1
90 parts, 4 parts of methyl methacrylate, 5 parts of styrene, 0.3 part of potassium carbonate and 0.3 part of tert-dodecylmercaotan (TDM), deionization
280 parts of water, 0.25 part of potassium peroxydisulfate be added in reaction kettle, be warming up to 60 DEG C of progress polymerization reactions；
(2) it when butadiene is reacted to conversion ratio >=95%, is heated up with 0.5 DEG C/min, to partial size agglomeration to 300nm
Stop reaction when left and right to get big partial size polybutadiene latex is arrived.
In step (2) of the present invention, when butadiene is reacted to conversion ratio >=95%, polybutadiene latex is obtained
Partial size is 92nm.
In step (2) of the present invention, big partial size polybutadiene latex, partial size 285nm.
Embodiment 7-10
According to the formula of table 2 and condition, embodiment 7-10 latex of polybutadiene in small grain size, remaining condition and implementation are prepared respectively
Example 6 is essentially identical, and raw material dosage is mass parts in table.
2 embodiment 6-10 raw material of table and parameter
Comparative example 1
Take 1.5 parts of potassium oleate, 1.5 parts of disproportionated rosin acid potassium, 90 parts of butadiene, 5 parts of methyl methacrylate, styrene 5
Part, 0.3 part of 0.3 part of potassium carbonate and tert-dodecylmercaotan (TDM), 280 parts of deionized water be added in reaction kettle, stirring is equal
It is even, be heated to 60 DEG C, 0.25 part of progresss polymerization reaction of potassium peroxydisulfate is added, it is poly- when butadiene is reacted to conversion ratio >=95%
Butadiene latex, partial size 95nm.
30 parts of above-mentioned latex is taken, the acetic acid and test sample process partial size of 6% mass concentration are slowly added to, to partial size agglomeration
When to 300nm or so, cools down rapidly, discharge after mixing evenly, actual particle size is 320nm, particle diameter distribution index after measuring discharging
PDI is 0.264.
Comparative example 2
Take 1.5 parts of potassium oleate, 1.5 parts of disproportionated rosin acid potassium, 90 parts of butadiene, 5 parts of methyl methacrylate, styrene 5
Part, 0.3 part of 0.3 part of potassium carbonate and tert-dodecylmercaotan (TDM), 280 parts of deionized water be added in reaction kettle, stirring is equal
It is even, be heated to 60 DEG C, 0.25 part of progresss polymerization reaction of potassium peroxydisulfate is added, it is poly- when butadiene is reacted to conversion ratio >=95%
Butadiene latex, partial size 95nm.
30 parts of above-mentioned latex is taken, is put into refrigerator and is cooled to -5 DEG C, is taken out after keeping the temperature 30min, is heated to 25 DEG C of holding 2h,
Measuring partial size is 786nm, and particle diameter distribution index is 1.
Comparative example 3
The preparation of butadiene latex:
Take 1.5 parts of potassium oleate, 1.5 parts of disproportionated rosin acid potassium, 90 parts of butadiene, 5 parts of methyl methacrylate, styrene 5
Part, 0.3 part of 0.3 part of potassium carbonate and tert-dodecylmercaotan (TDM), 280 parts of deionized water be added in reaction kettle, stirring is equal
It is even, be heated to 60 DEG C, 0.25 part of progresss polymerization reaction of potassium peroxydisulfate is added, it is poly- when butadiene is reacted to conversion ratio >=95%
Butadiene latex, partial size 95nm.
Macromolecule agglomerant is prepared referring to patent CN 102050889A:
By 150 parts of deionized water, 0.4 part of sodium bicarbonate, 4 parts of lauryl sodium sulfate, 0.5 part of potassium peroxydisulfate, dodecane
0.6 part of base mercaptan, 20 parts of butyl acrylate and 15 parts of styrene are added with blender, reflux condenser, four mouthfuls of thermometer
In flask, it is put into water-bath, is replaced after starting stirring and emulsifying with nitrogen, is warming up to 55 DEG C, starts timing, polymerization is added dropwise after 1 hour
Mix monomer, mix monomer include 40 parts of butyl acrylate, 15 parts of styrene, 10 parts of methacrylic acid, 2 parts of OP-10, reaction 2
Hour, 75 DEG C are raised the temperature to, being stirred for reaction in 1 hour terminates, and cools down, and filtering obtains macromolecule agglomerant.
Macromolecule agglomeration:
It takes 2 parts of above-mentioned macromolecule agglomerant to be added in 100 parts of polybutadiene latexs, is slowly stirred 10 minutes, it is small to place 4
When, after-agglomeration polybutadiene latex is obtained, measuring partial size is 450nm, particle diameter distribution index 0.358.
Embodiment 11
ABS powder grafting: 60 parts of after-agglomeration polybutadiene latex of gained (in terms of solid contain), 10 parts of propylene in Example 6
3 parts of disproportionated rosin acid potassium, 0.22 part of sodium pyrophosphate are added in nitrile, 30 parts of styrene, 0.31 part of tert-dodecylmercaotan, and opening is stirred
It mixes, after being warming up to 65 DEG C, 0.29 part of cumyl hydroperoxide, 0.0045 part of ferrous sulfate, 0.27 part of glucose is added, grafting is poly-
After closing reaction 180 minutes, polybutadiene latex (ABS lotion), agglomerates by dilute sulfuric acid after being grafted, deionized water washing,
Centrifugal dehydration obtains ABS grafting powder after roller drying.
Blending granulation prepares ABS resin: above-mentioned 24 parts of ABS are grafted powder and 76 parts of SAN resins 2437 (Jilin Petrochemical)
And 0.1 part of 0.1 part of antioxidant 618 (climb and spend chemical (Shanghai) Co., Ltd.) of antioxidant 1010 (German BASF), magnesium stearate
0.2 part, N, 2 parts of N- ethylene bis stearic acid amide (Shandong Li Ang new material Co., Ltd) mediates 5min in high-speed kneading machine,
Then mixed material is carried out melt pelletization blending in double screw extruder, is granulated, finally obtains ABS resin pellet.It will be upper
It is 2 hours dry in 80 DEG C of baking ovens to state pellet, carries out Mechanics Performance Testing.Performance detection data is as follows: Izod impact strength
185J/m, bending strength 59.2Mpa, bending modulus 2280Mpa, tensile strength 45.9Mpa, elongation at break 46%.
Embodiment 12-18
Embodiment 12-15, embodiment 16-18 are respectively to use in embodiment 7-10, comparative example 1-3 to gather after prepared agglomeration
Butadiene latex carries out the grafting of ABS powder and blending granulation prepares ABS resin and tested, and performance is as shown in table 3:
3 embodiment 11-18 raw material of table and parameter
Thermo-sensitive emulsifier of the present invention, can be used in the production of polybutadiene latex, can be used for polybutadiene
The polybutadiene agglomeration lotion of the agglomeration of latex, the narrow ditribution controlled by temperature (PDI < 0.2) partial size is grafted, is coagulated
The ABS grafting powder obtained after poly-, washing, dehydration, drying is granulated obtained ABS product and agglomeration technique ABS phase with the blending of SAN resin
It is more than 170J/m than impact strength, in the case where keeping tensile strength to be not less than agglomeration technique ABS, elongation at break is more than
60%, and bending strength and bending modulus all make moderate progress.
Claims (11)
1. a kind of emulsifier for the production polybutadiene latex that can be used for agglomeration, which is characterized in that the emulsifier includes hydrophilic
The sorb alcoholic extract hydroxyl group of property, amide groups and hydrophobic alkyl carbon chain, isopropyl.
2. emulsifier according to claim 1, which is characterized in that the emulsifier is by sorbierite single-hard ester acid ester
(Span60) esterification is carried out with acid anhydrides, then reacts the amidated products generated with isopropylamine again.
3. emulsifier according to claim 2, which is characterized in that the acid anhydrides is phthalic anhydride, succinic anhydride, penta
Dicarboxylic anhydride, adipic anhydride, diglycolic anhydride, 2,3- pyrazine diacid acid anhydride, 1,2- cyclohexyl dicarboxylic acid acid anhydride, 4- methyl hexahydrophthalic anhydride, 1,
One of 2- cyclohexyl dicarboxylic acid acid anhydride, 1,2- ring, penta dicarboxylic acid anhydride, 1,1- cyclohexanediacetic acid acid anhydride are a variety of, preferably O-phthalic
Acid anhydrides and/or succinic anhydride.
4. emulsifier according to claim 2, which is characterized in that the molar ratio of the acid anhydrides and Span60 are (0.9-1):
1, preferably (0.93-0.97): 1.
5. emulsifier according to claim 2, which is characterized in that the molar ratio of the isopropylamine and acid anhydrides is
(0.5-1): 1, preferably: (0.7-0.9): 1.
6. a kind of method for preparing emulsifier of any of claims 1-5, comprising the following steps:
(1) it is proportionally added into Span60 and organic solvent in the reactor, is heated to 70 DEG C -80 DEG C, preferably 73 DEG C -77 DEG C, presses
Acid anhydrides is added in reactor and carries out esterification by ratio；
(2) isopropylamine is added when residual carboxylic's radical content reaches consistent with acid anhydrides molal quantity is added in step (1) and mixes
Uniformly, reaction generates carboxylic acid amine salt, then removes organic solvent；
(3) 200 DEG C -260 DEG C, preferably 220 DEG C of -240 DEG C of progress acylation reactions, conversion ratio >=90% to isopropylamine are warming up to
When, maintain reactor in absolute pressure it is constant be 3Kpa-10Kpa, preferably 5Kpa-8Kpa, the reaction was continued, to product acid value maintain
When constant, emulsifier amidated products are obtained.
7. according to the method described in claim 6, the organic solvent is acetonitrile, ethyl acetate, tetrahydrofuran, propionic acid second
One of ester, propyl acetate are a variety of, ethyl acetate.
8. according to the method described in claim 6, the additional amount of the organic solvent and Span60, acid anhydrides, isopropylamine are total
The mass ratio of amount is (5-9): 1, preferably: (6-8): 1.
9. a kind of preparation method of polybutadiene latex comprising the steps of:
(1) any one of emulsifier of any of claims 1-5 or claim 6-8 the method emulsification obtained
Agent, disproportionated rosin acid potassium, potassium oleate, butadiene, optional second comonomer, potassium carbonate and tert-dodecylmercaotan (TDM), go from
Sub- water, potassium peroxydisulfate are added in reaction kettle, are warming up to 60 DEG C -75 DEG C, preferably 65 DEG C of -70 DEG C of progress polymerization reactions；
(2) when butadiene is reacted to conversion ratio >=95%, with 0.1 DEG C/min-, 0.5 DEG C/min, preferably 0.2 DEG C/min-0.4
DEG C/min heats up, stop reaction when partial size agglomeration to 300nm or so to get big partial size polybutadiene latex is arrived.
10. according to the method described in claim 9, its raw materials used quality dosage is as follows:
11. according to the method described in claim 9, the second comonomer is styrene, acrylonitrile and methyl methacrylate
One or more, optimization styrene and/or methyl methacrylate.
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Cited By (3)
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|---|---|---|---|---|
| CN110627929A (en) * | 2019-10-25 | 2019-12-31 | 长春工业大学 | Preparation method of micro-nano polymer water-based antioxidant emulsion |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627929A (en) * | 2019-10-25 | 2019-12-31 | 长春工业大学 | Preparation method of micro-nano polymer water-based antioxidant emulsion |
| CN113493530A (en) * | 2020-04-07 | 2021-10-12 | 万华化学集团股份有限公司 | Polybutadiene latex agglomeration method and application thereof |
| CN113493530B (en) * | 2020-04-07 | 2022-09-20 | 万华化学集团股份有限公司 | Polybutadiene latex agglomeration method and application thereof |
| CN113881003A (en) * | 2021-09-27 | 2022-01-04 | 万华化学(四川)有限公司 | ABS graft polymerizable emulsifier, preparation method and application thereof, and preparation method of ABS graft latex |
| CN113881003B (en) * | 2021-09-27 | 2024-02-27 | 万华化学(四川)有限公司 | ABS grafted polymerizable emulsifier, preparation method and application thereof, and preparation method of ABS grafted latex |
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